CN101965233A - Niobium as the protective wall in the motlten metal - Google Patents

Niobium as the protective wall in the motlten metal Download PDF

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Publication number
CN101965233A
CN101965233A CN2009801078373A CN200980107837A CN101965233A CN 101965233 A CN101965233 A CN 101965233A CN 2009801078373 A CN2009801078373 A CN 2009801078373A CN 200980107837 A CN200980107837 A CN 200980107837A CN 101965233 A CN101965233 A CN 101965233A
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China
Prior art keywords
niobium
internal layer
mould
skin
sensor
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Granted
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CN2009801078373A
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Chinese (zh)
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CN101965233B (en
Inventor
维克多·F·朗德基斯特
凯文·S·姬尔
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RUNDQUIST VICTOR F
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Southwire Co LLC
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Priority to CN201310003696.9A priority Critical patent/CN103056318B/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B06—GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
    • B06B—METHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
    • B06B3/00—Methods or apparatus specially adapted for transmitting mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B22D11/004—Copper alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/059—Mould materials or platings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D25/00—Special casting characterised by the nature of the product
    • B22D25/02—Special casting characterised by the nature of the product by its peculiarity of shape; of works of art
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Coating With Molten Metal (AREA)
  • Continuous Casting (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)

Abstract

The present invention discloses a kind of equipment that for example can contact with the motlten metal such as copper.Described equipment can include, but are not limited to be used for making the goods of making by motlten metal mould, be used for determining motlten metal solution gas amount sensor or be used to reduce the ultrasonic equipment of the gas content (as, hydrogen) of motlten metal.When these equipment were exposed to motlten metal, niobium can be as the protective wall of these equipment.

Description

Niobium as the protective wall in the motlten metal
Quoting of related application
The application as the pct international patent application to submit March 4 in 2009 as the applicant's of all designated states United States citizen Victor F.Rundquist and the name of United States citizen Kevin S.Gill, and require the U.S. Provisional Patent Application sequence number No.61/033 that submits on March 5th, 2008,807 priority.
Copyright
Be included in all authority of this material, comprise that copyright ownership is in applicant and the ownership that is.The applicant adheres to and keeps all authority of the material that is included in this, and only authorizes together with duplicating of the patent of authorizing and allow to duplicate this material, and is not used in other purpose.
Background technology
The processing of copper product or casting may need to comprise the electrolytic cell of molten copper, and the electrolytic cell of this molten copper may remain on the temperature about 1100 ℃.Multiple instrument or equipment are used for monitoring or testing the situation of molten copper in electrolytic cell, and the final manufacturing or the casting of the copper product that is used to expect.Have a kind of like this demand, wish that these instruments or equipment bear the temperature of the rising that runs in the molten copper electrolytic cell better, useful is to have the long life-span, and is limited not react with molten copper.
Summary of the invention
It is in order to be introduced in the selection of the notion that hereinafter further describes in detailed specification with simple form that content of the present invention is provided.Content of the present invention is not to determine the key feature or the essential feature of theme required for protection.Content of the present invention also is the scope that is not used for limiting theme required for protection.
Equipment for example may contact with the motlten metal such as copper.This equipment can include but not limited to be used for making the object of making by motlten metal mould, be used for determining motlten metal solution gas amount sensor or be used to reduce the ultrasonic equipment of the gas content (as, hydrogen) of motlten metal.When these equipment were exposed to motlten metal, niobium can be as the protective wall of these equipment.
The aforementioned summary of the invention and the ensuing specific embodiment have all only provided example and have been exemplary.Therefore, the aforementioned summary of the invention and the ensuing specific embodiment not will be understood that it is restrictive.And, except those features of this proposition, can also provide further feature or distortion.For example, each embodiment can relate to various feature combinations or the secondary combination of describing in the specific embodiment.
Description of drawings
Be combined in the accompanying drawing that also constitutes a part wherein in the disclosure and illustrate numerous embodiments of the present invention.In the accompanying drawings:
Fig. 1 shows the partial sectional view of mould;
Fig. 2 shows the partial sectional view of sensor; And
Fig. 3 shows the partial sectional view of ultrasonic equipment.
The specific embodiment
The ensuing specific embodiment relates to accompanying drawing.As possible, identical Reference numeral is used in accompanying drawing and the ensuing description to indicate identical or similar elements.Though can describe numerous embodiments of the present invention, modification, rewriting and other embodiment also are feasible.For example, can replace, add or revise illustrated element in the accompanying drawings, and can by replace, rearrangement or add a plurality of stages and method described here is made amendment to disclosed method.Therefore, the ensuing specific embodiment does not limit the present invention.
The embodiments of the present invention can provide the system and method in the life-span that is used for increasing the parts that directly contact with motlten metal.For example, the embodiments of the present invention can adopt niobium to reduce the degeneration of the material that contacts with motlten metal, cause the quality of final products to occur obviously improving.In other words, the embodiments of the present invention can adopt niobium to increase the material that contacts with motlten metal or the life-span of parts as protective wall, perhaps protect these materials or parts.Niobium can have various features, and for example, its fusing point is good, can help to provide aforementioned each embodiment of the present invention.In addition, when being exposed to 200 ℃ and above temperature, niobium can also form the protectiving oxide screen layer.
And the embodiments of the present invention can be provided for increasing the system and method in the life-span of the parts that directly contact or engage with motlten metal.Because niobium and motlten metal is reactive low, adopt niobium can prevent the backing material degeneration.The quality of the material that contacts with motlten metal may reduce the quality of final products.Therefore, the embodiments of the present invention can adopt niobium to reduce the degeneration of backing material, cause the quality of final products obviously to be improved.Therefore, the niobium that combines with motlten metal can in conjunction with the high-melting-point of niobium and with hypoergia such as the copper metal.
The embodiment consistent with the present invention can comprise the mould that comprises graphite and niobium.This mould can be used for from comprising the electrolytic cell vertical casting copper product of molten copper.For example, mould can comprise internal layer and skin, and its ectomesoderm can be configured to make heat to be delivered to the surrounding environment from the motlten metal such as molten copper.Internal layer can be configured to for skin provides screen layer, as barrier to oxygen.Internal layer can comprise niobium, and skin can comprise graphite.The niobium internal layer can be for directly contacting with motlten metal, for example, and the layer that contacts with molten copper.Comprise niobium internal layer thickness may to the thermal conductivity of mould and final function and niobium be provided at the screen layer on the graphite and the mould terminal life that produced very important.For example, do not have the graphite jig life-span of niobium may be about 3 days, and comprise that the graphite and the life-span of the mould of the niobium layer that directly contacts with molten copper can be about 15 to about 20 days.In some embodiments, comprise that the thickness of the internal layer of niobium can be less than about 10 microns, as from about 1 to about 10 microns scope.In other embodiment of the present invention, comprise that the thickness of the internal layer of niobium can be from about 2 to about 8 microns, or from about 3 to about 6 microns scope.
According to the embodiments of the present invention, niobium can be with the coating that acts on the mould of vertical casting in bronze in making.The shape of mould openings can be cylindrical shape substantially, but this is not requirement.The ensuing stage during vertical casting in bronze is made can comprise following process.At first, the vertical graphite jig of packing in the cooling collar can immerse in the molten copper electrolytic cell.Mould can be exposed to about 1100 ℃ temperature.Because graphite can have outstanding thermal conductivity, the graphite in the mould can make heat be delivered to the surrounding environment from molten copper.By this cooling procedure, molten copper can be converted into the solid copper bar.Yet aforementioned graphite jig may have high reactivity with oxygen (may be present in the molten copper), causes mould to be degenerated.Therefore, graphite jig may need periodically to change, to satisfy copper bar quality requirement.This may cause again making and quality cost higher.
Fig. 1 illustrates and adopts niobium as the barrier coatings in the graphite jig for example.As shown in Figure 1, the embodiments of the present invention can provide mould 100, and its high melt point that can utilize niobium and it and the hypoergia of molten copper increase the life-span (comparing with conventional graphite jig) of mould 100.For example, the embodiments of the present invention can be used the niobium coating on the graphite part of mould 100.Niobium can directly contact with molten copper.The niobium coating can reduce or anti-block is penetrated in the graphite, therefore increases the life-span of mould 100.This can cause the reduction of product cost and the increase of quality again.Consistent with the embodiments of the present invention, the niobium coating can be very thin, and still as the screen layer of oxygen, not with the molten copper reaction, and the thermal characteristics of mould 100 changes seldom or do not change (comparing with conventional graphite jig).In other words, the niobium coating that can select adequate thickness to be being provided with aforementioned barrier to oxygen, and enough thin, to allow mould 100 heat is delivered to the surrounding environment from molten copper.
Consistent with this embodiment is the method that is used for comprising from the molten copper manufacturing solid articles of copper.This method can comprise provides the electrolytic cell that comprises molten copper, molten copper is incorporated into the inlet of mould 100 and by mould 100 processing molten coppers, cooling is simultaneously made the solid articles that comprises copper with the exit at mould 100 from electrolytic cell.Can make goods by this method, and this goods also are parts of the present invention.For example, these goods can be for comprising the bar of copper.
In other embodiments, niobium can be used in the sensor of amount of solution gas of the electrolytic cell that is used for determining comprising molten copper.For example, sensor can comprise the sensor body of a part that centers on solid electrolyte tube and be included in the interior reference electrode of solid electrolyte tube.Solid electrolyte tube can comprise first end and the second end.The first end of solid electrolyte tube can be positioned in the sensor body, and the second end can comprise from the outward extending tip of sensor body.According to this embodiment, the tip of solid electrolyte tube can comprise niobium.The electrolytic cell that comprises molten copper can comprise solution gas, and solution gas for example can be the combination of oxygen, hydrogen or sulfur dioxide or these materials.This sensor can be used on continuous basis measuring the amount of the solution gas in the electrolytic cell of molten copper, replacedly, can be used for testing isolator or periodically with a certain predetermined time interval the amount of each solution gas.
Fig. 2 illustrates the amount that adopts the material of niobium as sensor 200, sensor 200 to be used for measuring continuously the oxygen of the electrolytic cell that comprises motlten metal, and described motlten metal includes but not limited to copper.Know that the oxygen content in the molten copper is useful at the casting in bronze fabrication technique.When copper solidifies, too much or oxygen very little may have injurious effects to goods or casting.For example, in the molten copper from about 150ppm to about 400ppm, perhaps from 175ppm extremely the oxygen content in the scope of about 375ppm may be favourable the casting in bronze fabrication technique.Though this sensor can be measured the amount of the dissolved oxygen in the 150-400ppm scope, can expect that this sensor has from being low to moderate about 50ppm to height to about 1000ppm or more can measure the detection range of oxygen content.
The lambda sensor 200 of Fig. 2 can comprise and hold or be included in reference electrode 250 in the solid electrolyte tube 230.Reference electrode 250 can be for the mixture of metal/metal oxide, as Cr/Cr 2O 3, it can set up the reference value of partial pressure of oxygen.The part of solid electrolyte tube 230 can be surrounded by insulating materials 220.Insulating materials 220 can comprise aluminium oxide (Al 2O 3) or the similar particle of insulating materials.Solid electrolyte tube 230 and insulating materials 220 can be surrounded by sensor body 210.Sensor body 210 can include but not limited to metal, pottery or plastics by multiple suitable material structure.The combination of these materials also can be used in the sensor body 210.The shape of sensor body 210 can be for general cylindrical shape, but this is not requirement.
In some embodiments, sensor body 210 can only center on the part of solid electrolyte tube 230.For example, solid electrolyte tube 230 can comprise first end and the second end.The first end of solid electrolyte tube 230 can be positioned in the sensor body, and the second end can comprise on the sensor body 210 outward extending most advanced and sophisticated 240.According to certain embodiments of the present invention, the tip 240 of solid electrolyte tube 230 can be placed in the electrolytic cell that comprises molten copper, to determine the oxygen content of dissolving.
Solid electrolyte tube 230, most advanced and sophisticated 240 or the two can comprise niobium.Niobium can form alloy with one or more other metals, and perhaps niobium can be the layer on plating or the basic unit that is coated in other material.For example, solid electrolyte tube 230, most advanced and sophisticated 240 or the two can comprise internal layer and skin, wherein internal layer can comprise pottery or metal material, skin can comprise niobium.Can be contemplated that niobium solid electrolyte tube 230, most advanced and sophisticated 240 or existence in the two intensity at fusion temperature place of good electrical conductivity, copper and the chemical erosion of anti-molten copper can be provided.Niobium can provide each embodiment with aforementioned features of the present invention, and processing and manufacturing are simple.Not shown in Figure 2, but what be contained in this is sensor output or read-out device, and it shows the oxygen content of measuring based on the signal of telecommunication that produces from sensor 200.This output or read-out device can physical connections or are wirelessly connected to sensor 200.
Consistent with this embodiment is is used for measuring the method for amount of the solution gas of the electrolytic cell that comprises molten copper.This method can comprise the tip 240 of sensor 200 inserted and comprise in the electrolytic cell of molten copper, and determines to comprise the amount of the solution gas in the electrolytic cell of molten copper according to the signal of telecommunication that is produced.Usually, measured solution gas is an oxygen.The amount that is dissolved in the oxygen in the electrolytic cell that comprises molten copper can be at about 50ppm to the scope of about 1000ppm, for example, and from about 150ppm scope of about 400ppm extremely.
In other embodiments, niobium can be used in the ultrasonic equipment that comprises ultrasonic transducer and seeker.Seeker can comprise first end and the second end, and wherein first end can be connected to ultrasonic transducer, and the second end can comprise the tip.According to this embodiment, the tip of seeker can comprise niobium.This ultrasonic equipment can be used in the ultrasonic wave degassing process.The electrolytic cell that can be used in the molten copper in the manufacturing of copper bar can comprise solution gas, as hydrogen.May there be injurious effects in the dissolved hydrogen that surpasses 3ppm to the quality of casting speed and copper bar.For example, the about 4ppm in the molten copper, about 5ppm, about 6ppm, about 7ppm or about 8ppm and higher hydrogen level may be harmful to.Hydrogen may enter the molten copper electrolytic cell because it is present in the atmosphere of top of the electrolytic cell that comprises molten copper, and perhaps it may reside in the copper charging that is used in the molten copper electrolytic cell and begins in the parent material.A method that removes hydrogen from molten copper is to use ultrasonic vibration.The instrument that is used in the ultrasonic vibration technology can comprise the hyperacoustic transducer of generation.What be connected to transducer is can be for ultrasonic wave being delivered to the probe in the electrolytic cell that comprises dissolved copper.By move ultrasonic equipment in comprising the electrolytic cell of dissolved copper, hydrogen content can be reduced to less than about 3ppm, for example, is reduced to the scope from about 2ppm to about 3ppm, or is reduced to less than about 2ppm.
Fig. 3 illustrates and adopts niobium as the material in the ultrasonic equipment 300, and this ultrasonic equipment 300 can be used for reducing the hydrogen content in the molten copper.The ultrasonic probe assembly 302 that ultrasonic equipment 300 can comprise ultrasonic transducer 360, be used to increase the booster 350 of output and be connected to transducer 360.Ultrasonic probe assembly 302 can comprise elongated ultrasonic probe 304 and ultrasonic wave medium 312.The shape of ultrasonic equipment 300 and ultrasonic probe 304 can be cylindrical shape substantially, but this is not requirement.Ultrasonic probe 304 can comprise first end and the second end, and wherein first end comprises the ultrasonic probe axle 306 that is connected to ultrasonic transducer 360.Ultrasonic probe 304 and ultrasonic probe axle 306 can be by multiple material structures.Exemplary material is passable, but is not limited to stainless steel, titanium etc. or its combination.The second end of ultrasonic probe 304 can comprise ultrasonic probe tip 310.Ultrasonic probe tip 310 can comprise niobium.Replacedly, most advanced and sophisticated 310 is in essence can constitutionally consistent with niobium or be made of niobium.Niobium can form alloy with one or more other metals, and perhaps niobium can be the layer on the basic unit of plating or being coated in other material.For example, most advanced and sophisticated 310 can comprise internal layer and skin, and wherein internal layer can comprise pottery or metal material (as, titanium), and skin can comprise niobium.In this embodiment, the outer field thickness that comprises niobium can be less than about 10 microns, replacedly, from about 2 to about 8 microns scope.For example, comprising the outer field thickness of niobium can be from about 3 to about 6 microns scope.
Ultrasonic probe axle 306 can be connected by connector 308 with ultrasonic probe tip 310.Connector 308 can be represented the device that is used for connecting axle 306 and most advanced and sophisticated 310.For example, axle 306 and most advanced and sophisticated 310 can bolt or is welded together.In one embodiment, connector 308 can represent that axle 306 comprises the depression screw thread, and most advanced and sophisticated 310 can be screwed on the axle 306.Be contemplated that ultrasonic probe axle 306 can comprise different materials with ultrasonic probe tip 310.For example, ultrasonic probe axle 306 can comprise titanium, and ultrasonic probe tip 310 can comprise niobium.
Referring again to Fig. 3, pipe 328, central tube 324, outer tube 320 and protection tube 340 in ultrasonic equipment 300 can comprise.These pipes can center at least a portion of ultrasonic probe 304, and usually can be by any suitable metal material structure.Can be contemplated that ultrasonic probe tip 310 will be placed in the electrolytic cell of dissolved copper; Yet, be contemplated that the part of protection tube 340 also can immerse in the molten copper.Therefore, protection tube 340 can comprise in titanium, niobium, carborundum or these materials more than a kind of combination.Be included in pipe and can be fluid 322,326 and 342 in 328,324,320 and 340, as shown in Figure 3.Described fluid can the cooling that can provide ultrasonic equipment 300 be provided, and especially, provide the cooling to ultrasonic probe most advanced and sophisticated 310 and protection tube 340 for liquid or gas (as, argon).
Ultrasonic equipment 300 can comprise end cap 344.End cap can bridge joint protection tube 340 and probe tip 310 between the gap, and can reduce or prevent that molten copper from immersing ultrasonic equipment 300.Be similar to protection tube 340, end cap 344 for example can by in titanium, niobium, carborundum or these materials more than a kind of composite construction.
Ultrasonic probe tip 310, protection tube 340 or end cap 344 or this three can comprise niobium.Niobium can form alloy with one or more other metals, and perhaps niobium can be the layer on the basic unit of plating or being coated in other material.For example, ultrasonic probe tip 310, protection tube 340 or end cap 344 or this three can comprise internal layer and skin, and wherein internal layer can comprise pottery or metal material, and skin can comprise niobium.Can be contemplated that the life-span that on the parts of ultrasonic equipment, exists niobium can improve this equipment, when contacting, provide low or do not have chemical reaction, be provided at the intensity at the fusion temperature place of copper, and have the ability of propagate ultrasound waves with molten copper.
The embodiments of the present invention can comprise the method for the hydrogen content that is used for reducing the electrolytic cell that comprises dissolved copper.This method can comprise the tip 310 of ultrasonic equipment 300 inserted and comprise in the electrolytic cell of dissolved copper, and with preset frequency operation ultrasonic equipment 300, wherein operates ultrasonic equipment 300 and reduced hydrogen content in the electrolytic cell that comprises dissolved copper.Usually, before operation ultrasonic equipment 300, the hydrogen that dissolves in molten copper is greater than 3ppm, greater than 4ppm, greater than 5ppm or greater than 6ppm.For example, the hydrogen content that comprises in the electrolytic cell of dissolved copper can be about scope of 4 to about 6ppm at hydrogen.The result of this ultrasonic wave degasification mode is reduced to level less than about 3ppm (or replacedly less than about 2ppm) with comprising hydrogen content in the electrolytic cell of dissolved copper.
According to the embodiments of the present invention, adopt niobium can solve demand listed above.Niobium can have as in the characteristic shown in the following table 1.
Table 1
Forge tensile strength 585 MPas
Forge hardness 160HV
Elastic modelling quantity 103 gpa
Modulus of shearing 37.5 gpa
Fusing point 2750K(2477℃，4491°F)
Symbol, atomicity Nb，41
Atomic wts 92.91g/mol
Density 8.57g/cc
Thermal conductivity (300K)53.7W/m-k
Thermal expansion (25℃)7.3μm/m-k
Though described the embodiments of the present invention, can have other embodiment.And, do not departing under the condition of the present invention, can revise the stage of any disclosed method by any way, comprise each rearrangement in stage and/or insert or delete a stage.Though this specification comprises some examples, protection scope of the present invention is represented by ensuing claim.And though with architectural feature and/or method this specification that moved distinctive language description, claim is not limited to above-mentioned feature or action.Or rather, above-mentioned concrete feature and action are disclosed as the example that is used for the embodiments of the present invention.

Claims (20)

1. ultrasonic equipment comprises:
Ultrasonic transducer; With
Seeker comprises first end and the second end, and first end is connected to ultrasonic transducer, and the second end comprises the tip, and wherein, the described tip of seeker comprises niobium.
2. ultrasonic equipment according to claim 1, wherein, seeker comprises stainless steel, titanium or its combination.
3. ultrasonic equipment according to claim 1, wherein, the described tip of seeker comprises internal layer and skin.
4. ultrasonic equipment according to claim 3, wherein, internal layer comprises titanium.
5. ultrasonic equipment according to claim 3, wherein, skin comprises niobium.
6. ultrasonic equipment according to claim 3, wherein, the outer field thickness that comprises niobium is less than about 10 microns.
7. ultrasonic equipment according to claim 3, wherein, the outer field thickness that comprises niobium from about 2 to about 8 microns scope.
8. ultrasonic equipment according to claim 3, wherein, the outer field thickness that comprises niobium from about 3 to about 6 microns scope.
9. mould comprises:
Skin is configured so that heat is delivered to the surrounding environment from motlten metal; With
Internal layer, being configured to provides oxygen barrier layer for skin.
10. mould according to claim 9, wherein, skin comprises graphite.
11. mould according to claim 9, wherein, internal layer comprises niobium.
12. mould according to claim 11, wherein, comprise niobium internal layer thickness from about 1 to about 10 microns scope.
13. mould according to claim 11, wherein, the thickness of internal layer that comprises niobium is less than about 10 microns.
14. mould according to claim 11, wherein, comprise niobium internal layer thickness from about 2 to about 8 microns scope.
15. mould according to claim 11, wherein, comprise niobium internal layer thickness from about 3 to about 6 microns scope.
16. mould according to claim 9, wherein, internal layer is configured to provide oxygen barrier layer for skin when mould is exposed to about 1100 ℃ temperature.
17. the sensor of the amount of the solution gas of an electrolytic cell that is used for determining comprising dissolved copper, this sensor comprises:
Sensor body is around the part of solid electrolyte tube;
Described solid electrolyte tube comprises first end and the second end, and first end is positioned in the sensor body, and the second end comprises outward extending tip on the sensor body; With
Reference electrode is included in the solid electrolyte tube, and wherein, the tip of solid electrolyte tube comprises niobium.
18. sensor according to claim 17, wherein, the tip of solid electrolyte tube comprises internal layer and skin, and internal layer comprises pottery or metal material, and skin comprises niobium.
19. sensor according to claim 17, wherein, solution gas is oxygen, hydrogen, sulfur dioxide or its combination.
20. sensor according to claim 17, wherein, solution gas is an oxygen.
CN2009801078373A 2008-03-05 2009-03-04 Niobium as a protective barrier in molten metals Expired - Fee Related CN101965233B (en)

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